CN115348854A - Curable compositions and methods of using curable compositions - Google Patents
Curable compositions and methods of using curable compositions Download PDFInfo
- Publication number
- CN115348854A CN115348854A CN202180025588.4A CN202180025588A CN115348854A CN 115348854 A CN115348854 A CN 115348854A CN 202180025588 A CN202180025588 A CN 202180025588A CN 115348854 A CN115348854 A CN 115348854A
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- CN
- China
- Prior art keywords
- curable composition
- meth
- composition
- acrylate
- curable
- Prior art date
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- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims description 12
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 12
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 239000000945 filler Substances 0.000 claims description 34
- 150000001412 amines Chemical class 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 230000005670 electromagnetic radiation Effects 0.000 claims description 4
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
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- 239000004332 silver Substances 0.000 claims description 3
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- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 58
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000005385 borate glass Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000248 cariostatic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 210000004268 dentin Anatomy 0.000 description 1
- 239000003975 dentin desensitizing agent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- WJSATVJYSKVUGV-UHFFFAOYSA-N hexane-1,3,5-triol Chemical compound CC(O)CC(O)CCO WJSATVJYSKVUGV-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical group 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 229960002429 proline Drugs 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000395 remineralizing effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Chemical class 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- RHUVFRWZKMEWNS-UHFFFAOYSA-M silver thiocyanate Chemical compound [Ag+].[S-]C#N RHUVFRWZKMEWNS-UHFFFAOYSA-M 0.000 description 1
- CYLMOXYXYHNGHZ-UHFFFAOYSA-M silver;propanoate Chemical compound [Ag+].CCC([O-])=O CYLMOXYXYHNGHZ-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical class [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
- A61K6/844—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Dental Preparations (AREA)
Abstract
The curable composition comprises at least one monomer comprising at least one (meth) acryloyl group and a photoinitiator system. The photoinitiator system comprises at least one type II photoinitiator and at least one cyclic beta-diketone represented by formula (I)
Or a tautomer thereof. R 1 Denotes an organic moiety having at least one free-radically polymerizable group. Each R 2 Independently of each otherRepresents H or an aliphatic group having from 1 to 12 carbon atoms and up to two of the atoms oxygen and sulfur, and n represents 1,2 or 3.
Description
Technical Field
The present disclosure relates broadly to curable compositions comprising a beta-diketone and a type II photoinitiator.
Background
Photo-initiated curing is used to produce many industrially important materials such as, for example, coatings, adhesives, restoratives, and sealants. The photo-initiated curing materials typically contain type I and/or type II photoinitiators. In each case, the application of light induces rapid curing. When irradiated with the correct wavelength, the type I photoinitiator fragment generates polymer-initiated free radicals. Type II photoinitiators can abstract H atoms upon absorption of light, thereby generating initiating free radical species. However, if there is no readily abstractable H-atom, then no initiation occurs.
For this reason, type II photoinitiators are usually paired with coinitiators having an abstractable H-atom to form a photoinitiator system. Common coinitiators are amine-based. However, in the presence of oxygen, amine-based co-initiators can oxidize and disadvantageously discolor the resulting material over time. In addition, amine-based co-initiators are typically acid sensitive, limiting their utility when acidic adhesion promoting monomers are in the polymerizable composition. In addition, excess or unused co-initiator may migrate and/or leach out of the cured composition over time.
Disclosure of Invention
Advantageously, the present inventors have found that certain non-amine based co-initiators having polymerizable (meth) acrylate functionality that can be used with acidic monomers can avoid amine based discoloration and polymerize into the polymer network during curing.
In one aspect, the present disclosure provides a curable composition comprising:
at least one monomer comprising at least one (meth) acryloyl group; and
a photoinitiator system comprising:
at least one cyclic beta-diketone of the formula
Or a tautomer thereof, wherein:
R 1 represents an organic moiety having at least one free-radically polymerizable group;
each R 2 Independently represents H or an aliphatic group having from 1 to 12 carbon atoms and up to two of the atoms of oxygen and sulfur; and is
n represents 1,2, or 3; and
at least one type II photoinitiator.
In some embodiments, the curable composition may be a curable dental composition that can be at least partially cured to provide, for example, a dental restorative composition or a dental adhesive composition.
The curable composition according to the present disclosure may be contacted with at least one substrate; and receiving sufficient actinic electromagnetic radiation to at least partially cure them.
As used herein:
the term "type II photoinitiator" refers to a compound in which absorption of electromagnetic radiation (e.g., ultraviolet and/or visible light) causes an excited electronic state in the type II photoinitiator that will extract hydrogen from the co-initiator and generate a free radical pair in the process.
The term "dental composition" refers to any composition that can be used in the dental field. By "dental composition" is meant an unfilled or filled (e.g., composite) material (e.g., dental or orthodontic material) capable of being applied or adhered to an oral surface. Dental compositions include, for example, adhesives (e.g., dental and/or orthodontic adhesives), cements (e.g., glass ionomer cements, resin-modified glass ionomer cements, and/or orthodontic cements), primers (e.g., orthodontic primers), restoratives (e.g., restorative filling materials), liners, sealants (e.g., orthodontic sealants), and coatings. Dental compositions are often used to bond dental articles to dental structures.
The term "substantially free" with respect to a component (e.g., an amine or metal chelate) means that the composition is free of the component as an essential feature. Thus, the components are not intentionally added to the composition by themselves or in combination with other components or ingredients of other components. Compositions that are substantially free of a component (e.g., resin) typically comprise the component in an amount of less than about 5 wt.%, less than about 1 wt.%, less than about 0.5 wt.%, or less than about 0.01 wt.%, based on the total weight of the composition or material. The composition may not comprise said components at all. However, the presence of a small amount of the component is sometimes unavoidable, for example, because of impurities contained in the raw materials used.
The term "(meth) acryl" is a shorthand term which refers to "acryl" and/or "methacryl". For example, a "(meth) acryloyloxy" group is a shorthand term referring to an acryloyloxy group (i.e., CH) 2 = CH-C (O) -O-) and/or a methacryloxy group (i.e. CH 2 ＝C(CH 3 )-C(O)-O-)。
The term "substituted" means that the hydrogen atom is replaced with another organic (e.g., alkyl, aryl, alkaryl, or aralkyl) or inorganic group (e.g., halide, hydroxyl, alkoxy); and is
The term "metal chelate" refers to a compound that is interposed between an organic moiety and a metal ion, wherein the metal ion has a formal charge of at least 2 +.
The features and advantages of the present disclosure will be further understood upon consideration of the detailed description and appended claims.
Detailed Description
Curable compositions according to the present disclosure comprise at least one monomer comprising at least one (meth) acryloyl group and a photoinitiator system. In many preferred embodiments, at least one monomer comprises at least two or at least 3 monomers comprising at least one (meth) acryloyl group.
In many embodiments of the present disclosure, monomers containing methacryloyl groups are preferred over those having acryloyl groups, although this is not required. In many embodiments, the polymerizable component preferably comprises one or more di-, tri-, tetra-and/or pentafunctional monomeric or oligomeric aliphatic, cycloaliphatic and/or aromatic (meth) acrylates.
The (meth) acryloyl group containing monomers are widely commercially available; for example, from Sartomer co, exton, pennsylvania and other suppliers. Suitable monomers may include mono (meth) acrylates, di (meth) acrylates, poly (meth) acrylates such as, for example, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, alkoxylated tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, bis [1- (2-acryloyloxy) ] -p-ethoxyphenyldimethyl methane, bis [1- (3-acryloyloxy-2-hydroxy) ] -p-propoxyphenyldimethyl methane, bis (trimethylolpropane) tetraacrylate, chlorinated polyester (meth) acrylate, diethylene glycol di (meth) acrylate, diglycidyl (meth) acrylate of bisphenol A, dodecyl (meth) acrylate, epoxide (meth) acrylate oligomers, ethoxylated or propoxylated glycerol tri (meth) acrylate, ethyl (meth) acrylate, ethylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, hexanediol di (meth) acrylate, hexyl (meth) acrylate, hydroxybutyl (meth) acrylate, butyl (meth) acrylate, hydroxy-functional caprolactone (meth) acrylate, hydroxyisopropyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isobutyl (meth) acrylate, isodecyl (meth) acrylate, isononyl (meth) acrylate, isooctyl (meth) acrylate, isopropyl (meth) acrylate, lauryl (meth) acrylate, methyl (meth) acrylate, n-butyl (meth) acrylate, neopentyl glycol di (meth) acrylate, n-hexyl (meth) acrylate, nonylphenol ethoxylate (meth) acrylate, octyl (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol triacrylate, poly (ethylene glycol) di (meth) acrylate, polybutadiene di (meth) acrylate, polyester (meth) acrylate oligomer, polyurethane di (meth) acrylate, siloxane (meth) acrylate oligomer, sorbitol hexyl acrylate, stearyl (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetratetetrahydrofurfuryl (meth) acrylate, triethylene glycol di (meth) acrylate, tris (hydroxyethyl) isocyanurate, tris (meth) isocyanurate, beta-carboxyethyl (meth) acrylate, 1,1,1-trimethylolpropane tri (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, hexane-2,4,6-triol tri (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-cyclohexanediol diacrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, (meth) acrylamide, N-dimethyl (meth) acrylamide, methylene bis- (meth) acrylamide, diacetone (meth) acrylamide, and combinations thereof.
The monomer containing at least one (meth) acryloyl group is typically present in the composition in an amount of at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 95, or even at least 98 weight percent based on the total weight of the composition, although this is not required.
The free radically polymerizable compound may comprise an acid functional monomer, where the acid functional group may be the acid itself (such as a carboxylic acid), or a portion may be a salt thereof (such as an alkali metal carboxylate). Useful acid functional monomers include, but are not limited to, those selected from ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphonic or phosphoric acids, and mixtures thereof. Examples of such compounds include those selected from the group consisting of: acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, maleic acid, oleic acid, beta-carboxyethyl (meth) acrylate, 2-sulfoethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, vinyl phosphonic acid, phosphate esters of polypropylene glycol monomethacrylate, and mixtures thereof. Due to their availability, acid functional monomers are typically selected from ethylenically unsaturated carboxylic acids (e.g., (meth) acrylic acids). When a stronger acid is desired, the acidic monomers can include ethylenically unsaturated sulfonic acids and ethylenically unsaturated phosphonic acids. The acid functional monomer, if present, is generally used in an amount of from 0.5 to 15 parts by weight, preferably from 1 to 15 parts by weight, most preferably from 5 to 10 parts by weight, based on 100 parts by weight total monomer, but this is not required.
The photoinitiator system comprises at least one cyclic beta-diketone containing (meth) acrylate groups in combination with a type II photoinitiator.
Useful (meth) acrylate group-containing cyclic beta-diketones are represented by the formula
Or a tautomer thereof (e.g., as shown below):
wherein R is 1 Denotes an organic moiety having at least one free-radically polymerizable group.
In some preferred embodiments, R 1 Having from 4 to 32 carbon atoms and optionally containing from 1 to 12 atoms selected fromO, N and combinations thereof. In some preferred embodiments, R 1 Having from 4 to 20 carbon atoms and optionally containing from 1 to 10 heteroatoms selected from O, N and combinations thereof. In some preferred embodiments, R 1 Having from 4 to 16 carbon atoms and optionally containing from 1 to 8 heteroatoms selected from O, N and combinations thereof. In some preferred embodiments, R 1 Has 4 to 12 carbon atoms and optionally contains 1 to 8 heteroatoms selected from O, N and combinations thereof. In some preferred embodiments, R 1 Having from 4 to 8 carbon atoms and optionally containing from 1 to 6 heteroatoms selected from O, N and combinations thereof. Exemplary organic moieties R 1 Illustrated in the examples contained below.
In some preferred embodiments, R 1 Containing a single (meth) acryloyl group. In other preferred embodiments, R 1 Contains at least two (meth) acryloyl groups.
Each R 2 Independently represent H or an aliphatic group having from 1 to 12 carbon atoms (preferably from 1 to 8, more preferably from 1 to 4, and more preferably 1 or 2 carbon atoms) and up to two of the oxygen and sulfur atoms. In many preferred embodiments, R 2 Represents an alkyl group having 1 to 4 carbon atoms, more preferably a methyl or ethyl group.
n represents 1,2, or 3, more preferably 1 or 2.
Combinations of cyclic beta-diketones containing (meth) acrylate groups may also be used.
Cyclic beta-diketones containing (meth) acrylate groups can be prepared, for example, by (meth) acrylation of the corresponding alcohols according to known methods (e.g., using (meth) acryloyl chloride). Likewise, methods for preparing the corresponding alcohols are within the ability of those of ordinary skill in the art.
Suitable type II photoinitiators are well known in the art of photocuring. Commercially important type II photoinitiators include: diaryl ketones (e.g., benzophenone, 4-methylbenzophenone, or 4-chlorobenzophenone); 1-phenylpropane-1,2-dione (PPD); thioxanthone (2-isopropylthioxanthone, 2-mercaptothioxanthone, 2,4-Diethylthioxanthone (DETX), 1-chloro-4-propoxythioxanthone (CPTX) and 2-Chlorothioxanthone (CTX) or 4-isopropylthioxanthone); camphorquinone; biphenyl acyl; naphthoquinones (e.g., 2,2' -bis (3-hydroxy-1,4-naphthoquinone)), anthraquinones (e.g., anthraquinone, 1,4-dihydroxyanthraquinone, 2-methylanthraquinone, or 2,6-dihydroxyanthraquinone), and 3-coumarone or combinations thereof. Other type II Photoinitiators are described in Green, A.W. (2010), "Commercial Photoinitiators", industrial Photoinitiators, technical guides, pp.86-91, CRC Press, taylor and Francis Group (Commercial Photoinitiators, industrial Photoinitiators, A Technical Guide (pp.86-91), CRC Press, taylor and Francis Group).
The absorption characteristics of the type II photoinitiator will generally be selected based at least in part on the desired wavelength of actinic radiation selected. Typically, the actinic radiation will be in the ultraviolet (i.e., 200 nm to less than 400 nm) and/or visible (i.e., 400 nm to 700 nm) wavelength ranges, although this is not required. The preferred wavelength range is 250 nm to 450 nm.
The photoinitiator system may be used in any amount, preferably from 0.01 to 10 weight percent, more preferably from 0.1 to 5 weight percent, and more preferably from 0.1 to 2 weight percent, based on the total weight of the curable composition. The weight ratio of cyclic beta-diketone to type II photoinitiator will vary with the materials selected but is within the ability of one of ordinary skill in the art.
As previously mentioned, amines can produce aesthetically unacceptable discoloration over time. Thus, in many preferred embodiments, the curable composition is substantially free or free of organic amines. Likewise, the curable composition is preferably substantially free or free of beta-diketone (cyclic and/or acyclic) polyvalent metal complexes, which may also lead to coloration.
Curable compositions according to the present disclosure may contain silver (e.g., in the form of a silver salt, colloidal silver, or silver oxide). Examples of suitable silver salts include silver chloride, silver bromide, silver iodide, silver acetate, silver propionate, silver fluoride, silver nitrate, silver thiocyanate, silver fluoride diamine, silver iodide complex compounds, silver phosphate, or combinations thereof.
Compositions according to the present disclosure may contain a filler (i.e., one or more fillers). The filler may be selected to enhance certain characteristics such as compressive strength, radial tensile strength, abrasion resistance, appearance, translucency, radio opacity and storage stability of the dental material, as well as to limit exothermic effects during the initial curing stage. Optionally, to enhance the bond between the filler and the resin system, the surface of the filler particles may be treated with a surface treatment such as a silane coupling agent. The coupling agent may be functionalized with reactive curing groups such as acrylates and/or methacrylates. The filler may be selected from one or more of a variety of materials suitable for incorporation in compositions for dental applications, such as, for example, fillers currently used in dental restorative compositions.
The filler may be an inorganic material. Examples of suitable inorganic fillers include naturally occurring or synthetic materials such as quartz, nitrides (e.g., silicon nitride), glasses derived from, for example, ce, sb, sn, zr, sr, ba, or Al, colloidal silica, feldspar, borosilicate glass, kaolin, talc, titanium dioxide, zirconia and zinc glasses, zirconia-silica fillers; low mohs hardness fillers such as those described in U.S. Pat. No. 4,695,251 (Randklev); and submicron silica particles (e.g., fumed silica such as those available under the trade name "AEROSIL", such as "OX 50", "AEROSIL 130", "AEROSIL200", "AEROSIL 380" from Evonik, parsippany, new Jersey, usa, and "Cab-O-Sil M5" silica from Cabot corp., boston, massachusetts). Non-acid-reactive inorganic filler particles include quartz (i.e., silica), submicron silica, zirconia, submicron zirconia, and non-glass microparticles of the type described in U.S. Pat. No. 4,503,169 (Randklev). The filler may be a crosslinked organic material that is insoluble in the polymerizable resin, and is optionally filled with an inorganic filler. The filler is generally non-toxic and suitable for use in the mouth. The filler may be radiopaque, radiolucent, or non-radiopaque. Fillers used in dental applications are typically ceramic in nature.
The filler may also be an acid-reactive filler. Suitable acid-reactive fillers include metal oxides, glasses, and metal salts. Typical metal oxides include barium oxide, calcium oxide, magnesium oxide, and zinc oxide. Typical glasses include borate glasses, phosphate glasses, and untreated or silanol-treated fluoroaluminosilicate ("FAS") glasses. When placed in the oral environment, FAS glass has the added benefit of releasing fluoride at the dental treatment site. The FAS glass typically contains sufficient elutable cations such that when the glass is mixed with the components of the hardenable composition, a hardened dental composition will be formed. The glass also typically contains sufficient elutable fluoride ions so that the hardened composition will have cariostatic properties. The glass may be prepared from a melt containing fluoride, alumina and other glass forming ingredients using techniques familiar to those skilled in the art of FAS glass manufacture. FAS glasses are typically in the form of particles that are sufficiently finely divided so that they can be conveniently mixed with other cement components and the resulting mixture works effectively when used in the mouth.
Generally, the average particle size (typically referred to as diameter) of the FAS glass is no greater than 12 microns, typically no greater than 10 microns, and more typically no greater than 5 microns, as measured using, for example, a sedimentation particle size analyzer. Suitable FAS glasses will be familiar to those skilled in the art, are available from a variety of commercial sources, and many are found in currently available glass ionomer cements, such as those commercially available under the following trade names: VITREMER, VITREBOND, RELYX LUTING CEMENT, RELYX LUTING PLUS CEMENT, PHOTOAC-FIL QUICK, KETAC-MOLAR, and KETAC-FIL PLUS (3M ESPE Dental products, st. Paul, minnesota), FUJI II LC and FUJI IX (Tokyo GC Corporation, tokyo, japan)), and CHEMFIL Superior (Dentsply International, york, pennsylvania, of York, yonsylvania, york, yongpo, minn.). Mixtures of fillers may be used if desired.
Other suitable fillers are disclosed in U.S. Pat. Nos. 6,387,981 (Zhang et al) and 6,572,693 (Wu et al), and PCT International publication No. WO 01/30305 (Zhang et al), U.S. Pat. No. 6,730,156 (Windisch et al), WO 01/30307 (Zhang et al), and WO 03/063804 (Wu et al). The filler components described in these references include nanoscale silica particles, nanoscale metal oxide particles, and combinations thereof. Nanofillers are also described in U.S. patent nos. 7,090,721 (Craig et al), 7,090,722 (Budd et al) and 7,156,911; and U.S. Pat. No. 7,649,029 (Kolb et al).
Examples of suitable organic filler particles include, for example, filled or unfilled powdered polycarbonate, polyepoxide, and poly (meth) acrylate. Common dental filler particles are quartz, submicron silica, and non-glassy microparticles of the type described in U.S. Pat. No. 4,503,169 (Randklev).
Mixtures of these fillers as well as combination fillers made of organic and inorganic materials may also be used.
The filler may be particulate or fibrous in nature. The particulate filler may be generally defined as having an aspect ratio or aspect ratio of 20. A fiber can be defined as having an aspect ratio of greater than 20, or more commonly greater than 100. The shape of the particles may vary from spherical to ellipsoidal, or more planar, such as flakes or discs. The macroscopic properties may be highly dependent on the shape of the filler particles, and in particular the uniformity of the shape. Suitable optional fillers can be finely divided into particles having an average particle size (i.e., the longest dimension of the particle, such as the diameter) of no greater than about 10 microns and a maximum particle size of no greater than about 50 microns, although this is not required. The filler can have a unimodal or multimodal (e.g., bimodal) particle size distribution.
In some preferred embodiments, the dental composition comprises silica nanoparticles. Suitable nanosilicas are commercially available under the trade name NALCO COLLOIDAL silica from NALCO Chemical co, naperville, illinois. For example, preferred silica particles may be obtained using NALCO products 1040, 1042, 1050, 1060, 2327 and 2329.
The silica particles are preferably made from an aqueous colloidal dispersion of silica (i.e., a sol or hydrosol). The concentration of colloidal silica in the silica sol is typically about 1 to 50 weight percent. Colloidal silica sols that can be used are commercially available, having different colloidal sizes, see Matijevic, e.surface & Colloid Science, vol.6, ed., wiley John Sons,1973 (Matijevic, e., "surface and Colloid Science, vol.6, john wil international publishing company, 1973). Preferred silica sols for use in preparing the filler are provided as dispersions of amorphous silica in an aqueous medium, such as Nalco colloidal silica manufactured by Nalco Chemical Company, and those sols having a low sodium concentration that can be acidified by mixing with a suitable acid, such as LUDOX colloidal silica manufactured by dupont de Nemours & co or Nalco 2326 from Nalco Chemical Company. Preferably, the silica particles in the sol have an average particle size of about 5 to 100 nanometers (nm), more preferably 10 to 50nm, and most preferably 12 to 40 nm.
In some embodiments, the dental composition comprises zirconia nanoparticles. Suitable nanoscale zirconia nanoparticles can be prepared using hydrothermal techniques as described in U.S. Pat. No. 7,241,437 (Davidson et al).
In some embodiments, the total amount of filler is from about 2% to about 90% by weight, based on the total weight of the components of the dental material. In certain embodiments, the total amount of filler is from about 30% to about 85% by weight, based on the total weight of the components of the dental material. The optional filler can be present in any suitable amount (e.g., 10 to 90 weight percent of the curable composition, preferably 10 to 60 weight percent of the curable composition).
Curable compositions according to the present disclosure may comprise one or more additional components such as, for example, solvents, antioxidants, flavoring agents, fluorinating agents, buffering agents, numbing agents, remineralizing agents, desensitizing agents, coloring agents, indicators, viscosity modifiers, surfactants, stabilizers, preservatives (e.g., benzoic acid), or combinations thereof.
The curable composition according to the present disclosure may be used as a dental composition. The dental composition is typically a hardenable composition that can be hardened at ambient conditions including a temperature range of about 15 ℃ to 50 ℃ or about 20 ℃ to 40 ℃ in a time range of about 30 minutes or 20 minutes or 10 minutes or 1 minute or less. Higher temperatures are not recommended because they may cause pain to the patient and may be harmful to the patient's health. Dental compositions are typically provided to practitioners in comparably small volumes, i.e. volumes in the range of about 0.1ml to about 100ml or about 0.5ml to about 50ml or about 1ml to 30 ml. Thus, the storage volumes of the available packaging units are within these ranges.
Curable compositions according to the present disclosure may be applied to at least one substrate and then cured using actinic radiation. Exemplary radiation sources include LED lamps (e.g., at 365nm, 385nm, 405nm, or 450 nm), arc lamps (e.g., hg or Xe arc lamps), flash lamps (e.g., xe flash lamps), ultraviolet or visible wavelength lasers (e.g., excimer, solid-state, pulsed, and/or CW lasers), and microwave-driven type H, D, or V mercury lamps (e.g., sold by Heraeus Noblelight America, gaithersburg, maryland). Filters and/or dichroic mirrors, for example, may also be used to reduce the thermal energy associated with the actinic radiation. The selection of curing conditions is within the ability of one of ordinary skill in the art.
Exemplary substrates may comprise metal, glass, ceramic, wood, plastic, fiber composites, enamel and/or dentin, and combinations thereof.
Selected embodiments of the present disclosure
In a first embodiment, the present disclosure provides a curable composition comprising:
at least one monomer comprising at least one (meth) acryloyl group; and
a photoinitiator system comprising:
at least one cyclic beta-diketone of the formula
Or a tautomer thereof, wherein:
R 1 represents an organic moiety having at least one free-radically polymerizable group;
each R 2 Independently represents H or an aliphatic group having from 1 to 12 carbon atoms and up to two of the atoms of oxygen and sulfur; and is
n represents 1,2, or 3; and
at least one type II photoinitiator.
In a second embodiment, the present disclosure provides the curable composition of the first embodiment, wherein the curable composition does not contain an organic amine.
In a third embodiment, the present disclosure provides the curable composition of the first or second embodiment, wherein the curable composition is free of at least one polyvalent metal complex of a cyclic β -diketone.
In a fourth embodiment, the present disclosure provides the curable composition of any one of the first to third embodiments, wherein the curable composition comprises silver.
In a fifth embodiment, the present disclosure provides the curable composition of any one of the first to fourth embodiments, further comprising a filler.
In a sixth embodiment, the present disclosure provides the curable composition of any one of the first to fifth embodiments, wherein the at least one type II photoinitiator comprises at least one of camphorquinone or isopropylthioxanthone.
In a seventh embodiment, the present disclosure provides the method according to any one of the first to sixth embodimentsThe curable composition of (1), wherein R 1 Having from 4 to 32 carbon atoms and optionally containing from 1 to 12 heteroatoms selected from O, N and combinations thereof.
In an eighth embodiment, the present disclosure provides the curable composition of any one of the first to seventh embodiments, wherein R 1 Having from 4 to 20 carbon atoms and optionally containing from 1 to 10 heteroatoms selected from O, N and combinations thereof.
In a ninth embodiment, the present disclosure provides the curable composition of any one of the first to eighth embodiments, wherein R 1 Containing a single free radical polymerizable group.
In a tenth embodiment, the present disclosure provides the curable composition of any one of the first to eighth embodiments, wherein R 1 Containing two free-radically polymerizable groups.
In an eleventh embodiment, the present disclosure provides a curable composition according to any one of the first to tenth embodiments, wherein the curable composition comprises a curable dental composition.
In a twelfth embodiment, the present disclosure provides a method of making an at least partially cured composition, the method comprising:
contacting the curable composition according to any one of the first to eleventh embodiments with at least one substrate; and
subjecting the curable composition to sufficient actinic electromagnetic radiation to provide the at least partially cured composition.
In a thirteenth embodiment, the present disclosure provides an at least partially cured composition made by the method according to the twelfth embodiment.
In a fourteenth embodiment, the present disclosure provides an at least partially cured composition according to the thirteenth embodiment, the at least partially cured composition herein comprising a dental composition.
Objects and advantages of this disclosure are further illustrated by the following non-limiting examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure.
Examples
All parts, percentages, ratios, and the like in the examples and the remainder of the specification are by weight unless otherwise indicated. Table 1 below reports the materials and light sources used in the examples.
TABLE 1
Synthesis of 2- (4-hydroxybenzyl) cyclohexane-1,3-Dione (DOH)
To a round bottom flask was added 1,3-cyclohexanedione (32.02g, 1.000 equivalents), 4-hydroxybenzaldehyde (34.85g, 1.000 equivalents), L-proline (13.15g, 0.4000 equivalents), and ethanol (1.428L). The reaction was stirred at room temperature for 45min. Then, naBH was added in 2g portions over 10 minutes 3 CN (17.95g, 1.000 equiv). The heterogeneous mixture was heated to 80 ℃ and stirred for 18 hours. Most of the ethanol was removed under reduced pressure to give an orange viscous oil, which was dissolved in ethyl acetate (200 mL), quenched with HCl solution (1m, 200ml) and stirred until bubbling ceased. The organic layer was separated and washed with HCl solution (1M, 3X 100 mL) and brine (2X 100 mL). The organic layers were collected, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to give an orange oil which was crystallized from hot ethyl acetate (100 mL) to give DOH (25.9 g) as a pale orange solid.
Synthesis of 2- (((4- ((2,6-dioxocyclohexyl) methyl) phenoxy) carbonyl) amino) ethyl methacrylate (DCMA)
DOH (5.00g, 1.00 eq) was dissolved in dry tetrahydrofuran (60 mL) in a flask equipped with a stir bar and stirred for 2 minutes. Triethylamine (3.19mL, 1.00 equiv) was then added, and some precipitate formed. The mixture was stirred for an additional 2 minutes, then IEM (3.24mL, 1.00 equiv.) and BHT (224 mg) were added and stirred at room temperature for 60 minutes. The orange solution was then concentrated under room atmosphere overnight (18 hours) to give an orange viscous oil, which was purified by column chromatography using a gradient eluent from 80/20 to 20/80 hexane/ethyl acetate (v/v). The desired fractions were collected, BHT (10 mg) was added, and the solvent was removed under reduced pressure to give DCMA as a white powder (3.39 g).
Examples EX-1 to EX-13 and comparative examples CE-A to CE-G
For the examples in table 2, the materials were combined to produce the inventive and comparative examples in the table below. An aliquot of the formulation was placed on a glass slide, illuminated with a light source (specified in table 2), and immediately evaluated by poking with a wooden spatula to determine if the formulation had cured (hard, brittle solids), partially cured (gel formed) or remained uncured (liquid).
TABLE 2
| Material | EX-1 | CE-A | CE-B1 | CE-B2 | EX-2 | CE-C |
| DCMA | 1.2 | 0 | 1.2 | 1.5 | 2 | 0 |
| SR339 | 33 | 36.8 | 33.5 | 34.6 | 38.2 | 34.7 |
| SR350 | 64.3 | 61.9 | 65.3 | 63.9 | 59.1 | 64.7 |
| ITX | 1.5 | 1.3 | - | - | - | - |
| CPQ | - | - | - | - | 0.7 | 0.6 |
| 365LED | Is that | Is that | Is that | - | - | - |
| Blue LED | - | - | - | Is that | Is that | Is that |
| Results | Has been cured | Not solidified | Not cured | Not cured | Has already solidified | Not cured |
For the examples in tables 3 and 4, the materials were combined to produce the inventive and comparative examples in the following tables. An aliquot of the formulation was placed on a glass slide, illuminated with a blue LED light source (described in table 1), and immediately evaluated by poking with a wooden spatula to determine if the formulation had cured (hard, brittle solids), partially cured (gel formed) or remained uncured (liquid).
TABLE 3
| Material | CE-D | CE-E | EX-3 | EX-4 | EX-5 | EX-6 |
| DCMA | 0.00 | 0.00 | 1.96 | 1.81 | 1.96 | 1.77 |
| CPQ | 0.24 | 0.24 | 0.23 | 0.22 | 0.23 | 0.21 |
| EDMAB | 0.40 | 0.48 | ||||
| HEMA | 39.60 | 29.70 | 48.91 | 45.28 | ||
| BisGMA | 8.30 | 29.70 | 48.91 | 45.28 | 27.91 | 25.21 |
| TEGDMA | 3.60 | |||||
| GDMA | 7.90 | |||||
| Procrylat K | 55.81 | 50.43 | ||||
| DDDMA | 13.96 | 12.61 | ||||
| BHT | 0.14 | 0.13 | ||||
| AgI | 12.44 | 12.38 | 2.30 | 3.00 | ||
| NH 4 I | 12.56 | 12.50 | 2.32 | 3.03 | ||
| NH 4 F | 1.96 | 1.95 | 0.36 | 0.47 | ||
| Water (W) | 13.08 | 13.01 | 2.42 | 3.15 | ||
| Results | Not cured | Not cured | Has already solidified | Partially curing | Has been cured | Has been cured |
TABLE 4
The preceding description, given to enable one of ordinary skill in the art to practice the claimed disclosure, is not to be construed as limiting the scope of the disclosure, which is defined by the claims and all equivalents thereto.
Claims (14)
1. A curable composition comprising:
at least one monomer comprising at least one (meth) acryloyl group; and
a photoinitiator system, the photoinitiator system comprising:
at least one cyclic beta-diketone of the formula
Or a tautomer thereof, wherein:
R 1 represents an organic moiety having at least one free-radically polymerizable group;
each R 2 Independently represent H or an aliphatic group having from 1 to 12 carbon atoms and up to two of the oxygen and sulfur atoms; and is
n represents 1,2, or 3; and
at least one type II photoinitiator.
2. The curable composition of claim 1, wherein the curable composition is free of an organic amine.
3. The curable composition of claim 1, wherein the curable composition is free of polyvalent metal complexes of the at least one cyclic beta-diketone.
4. The curable composition of claim 1, wherein the curable composition comprises silver.
5. The curable composition of claim 1, further comprising a filler.
6. The curable composition of claim 1, wherein the at least one type II photoinitiator comprises at least one of camphorquinone or isopropylthioxanthone.
7. The curable composition of claim 1, wherein R 1 Having from 4 to 32 carbon atoms and optionally containing from 1 to 12 heteroatoms selected from O, N and combinations thereof.
8. The curable composition of claim 1, wherein R 1 Has 4 to 20 carbon atoms, andand optionally containing 1 to 10 heteroatoms selected from O, N and combinations thereof.
9. The curable composition of claim 1, wherein R 1 Containing a single free radical polymerizable group.
10. The curable composition of claim 1, wherein R 1 Containing two free-radically polymerizable groups.
11. The curable composition of claim 1, wherein the curable composition comprises a curable dental composition.
12. A method of making an at least partially cured composition, the method comprising:
contacting the curable composition of claim 1 with at least one substrate; and
subjecting the curable composition to sufficient actinic electromagnetic radiation to provide the at least partially cured composition.
13. An at least partially cured composition prepared by the method of claim 12.
14. The at least partially cured composition of claim 13, wherein the at least partially cured composition comprises a dental composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202063006842P | 2020-04-08 | 2020-04-08 | |
| US63/006,842 | 2020-04-08 | ||
| PCT/IB2021/052823 WO2021205326A1 (en) | 2020-04-08 | 2021-04-05 | Curable compositions and methods of using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115348854A true CN115348854A (en) | 2022-11-15 |
| CN115348854B CN115348854B (en) | 2024-09-10 |
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| CN202180025588.4A Active CN115348854B (en) | 2020-04-08 | 2021-04-05 | Curable composition and method of using the curable composition |
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| Country | Link |
|---|---|
| US (1) | US20230119465A1 (en) |
| EP (1) | EP4132452B1 (en) |
| CN (1) | CN115348854B (en) |
| WO (1) | WO2021205326A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102985052A (en) * | 2010-07-02 | 2013-03-20 | 3M创新有限公司 | Dental composition, kit of parts and use thereof |
| CN103370041A (en) * | 2011-02-15 | 2013-10-23 | 3M创新有限公司 | Dental compositions comprising ethylenically unsaturated addition-fragmentation agent |
| WO2016014218A1 (en) * | 2014-07-22 | 2016-01-28 | 3M Innovative Properties Company | Free-radical polymerization methods and articles thereby |
| JP2016113438A (en) * | 2014-12-18 | 2016-06-23 | クラレノリタケデンタル株式会社 | Dental curable composition |
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|---|---|---|---|---|
| US4695251A (en) | 1980-04-07 | 1987-09-22 | Minnesota Mining And Manufacturing Company | Orthodontic bracket adhesive and abrasive for removal thereof |
| US4503169A (en) | 1984-04-19 | 1985-03-05 | Minnesota Mining And Manufacturing Company | Radiopaque, low visual opacity dental composites containing non-vitreous microparticles |
| US6730156B1 (en) | 1999-10-28 | 2004-05-04 | 3M Innovative Properties Company | Clustered particle dental fillers |
| US6572693B1 (en) | 1999-10-28 | 2003-06-03 | 3M Innovative Properties Company | Aesthetic dental materials |
| US6387981B1 (en) | 1999-10-28 | 2002-05-14 | 3M Innovative Properties Company | Radiopaque dental materials with nano-sized particles |
| EP1586294B2 (en) | 1999-10-28 | 2016-02-17 | 3M Innovative Properties Company | Nano-sized silica particles in a dry powder form |
| AU2003209430B2 (en) | 2002-01-31 | 2008-09-11 | 3M Innovative Properties Company | Dental pastes, dental articles, and methods |
| JP4127104B2 (en) * | 2002-04-03 | 2008-07-30 | Ｄｉｃ株式会社 | Photopolymerization initiator, novel compound and photocurable composition |
| US7649029B2 (en) | 2004-05-17 | 2010-01-19 | 3M Innovative Properties Company | Dental compositions containing nanozirconia fillers |
| US7090721B2 (en) | 2004-05-17 | 2006-08-15 | 3M Innovative Properties Company | Use of nanoparticles to adjust refractive index of dental compositions |
| US7090722B2 (en) | 2004-05-17 | 2006-08-15 | 3M Innovative Properties Company | Acid-reactive dental fillers, compositions, and methods |
| US7156911B2 (en) | 2004-05-17 | 2007-01-02 | 3M Innovative Properties Company | Dental compositions containing nanofillers and related methods |
| US7241437B2 (en) | 2004-12-30 | 2007-07-10 | 3M Innovative Properties Company | Zirconia particles |
| WO2008082881A1 (en) * | 2006-12-28 | 2008-07-10 | 3M Innovative Properties Company | (meth)acryloyl-containing materials, compositions, and methods |
-
2021
- 2021-04-05 CN CN202180025588.4A patent/CN115348854B/en active Active
- 2021-04-05 EP EP21723795.7A patent/EP4132452B1/en active Active
- 2021-04-05 WO PCT/IB2021/052823 patent/WO2021205326A1/en unknown
- 2021-04-05 US US17/911,569 patent/US20230119465A1/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102985052A (en) * | 2010-07-02 | 2013-03-20 | 3M创新有限公司 | Dental composition, kit of parts and use thereof |
| CN103370041A (en) * | 2011-02-15 | 2013-10-23 | 3M创新有限公司 | Dental compositions comprising ethylenically unsaturated addition-fragmentation agent |
| WO2016014218A1 (en) * | 2014-07-22 | 2016-01-28 | 3M Innovative Properties Company | Free-radical polymerization methods and articles thereby |
| JP2016113438A (en) * | 2014-12-18 | 2016-06-23 | クラレノリタケデンタル株式会社 | Dental curable composition |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021205326A1 (en) | 2021-10-14 |
| EP4132452B1 (en) | 2024-05-29 |
| US20230119465A1 (en) | 2023-04-20 |
| CN115348854B (en) | 2024-09-10 |
| EP4132452A1 (en) | 2023-02-15 |
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